Condensation products of sugar acid lactones with aromatic hydrocarbons



CONDENSATION PRODUCTS OF SUGAR ACID LACTONES WITH AROMATIC HYDROCAR-BONS Carl B. Linn, Riverside, Ill., assignor, by mesne assignments, toUniversal Oil Products Company, Des Plaines, 111., a corporation ofDelaware No Drawing. Filed May 9, 1957, Ser. No. 658,002 13 Claims. (Cl.260-3436) This application is a continuation-in-part of my copendingapplication Serial No. 450,222, filed August 16, 1954, now abandoned.

This invention relates to a new and useful process for condensing sugaracid lactones with aromatic hydrocarbo'ns in the presence of aFriedel-Crafts metal halide catalyst and to the products or novelcompositions of matter formed by said condensation. formed by mycondensation of sugar acid lactones with aromatic hydrocarbons areuseful per se, and are also useful as intermediates in the manufactureof detergents, pharmaceuticals, surface coatings, resins, gellingagents, corrosion inhibitors, and the like.

For example, the lactone of 1,1-di-phenyl-1-desoxyglucuronic acid,formed by the condensation of glucuronolactone with benzene, can beconverted to a so-called sugar detergent by ester exchange with methyllaurate, methyl myristate, methyl palmitate, methyl oleate, or methylstearate. These ester exchange reactions, as described in Industrial &Engineering Chemistry 48, 1459- 1464 (1956), are preferably carried outin dimethylformamide solution utilizing potassium carbonate or sodiummethoxide as the catalyst. As is observable from this publication, thepreparation of detergents from sugar de- Iivatives may be carried outreadily by one skilled in the art.

More specifically, this invention relates to a process for producingaryl-substituted polyhydroxycarboxylic acids, and salts and lactonesthereof. These lactones are internal esters of saidpolyhydroxycarboxylic acids, formed by the loss of water by interactionof a hydroxyl group with the carboxylic acid group of a given moleculeof a polyhydroxycarboxylic acid, with the resultant formation offuranose or pyranose ring systems or lactones.

An object of this invention is to condense an aromatic hydrocarbon witha lactone of a sugar acid in the presence of a Friedel-Crafts metalhalide catalyst, and to recover the products of said condensation.

Another object of this invention is to condense an aromatic hydrocarbonwith glucuronolactone, and torecover the product of said condensation.

A still further object of this invention is to condense benzene withglucuronolactone and to recover the product of said condensation.

One embodiment of this invention relates toa' process which comprisescondensing an aromatic hydrocarbon with a lacto'ne of a sugar acid inthe presence of a Friedel- Crafts metal halide catalyst, and recoveringthe resultant condensation product.

Another embodiment of this invention relates to a process whichcomprises condensing an aromatic hydrocarbon with a lactone of a sugaracid in the presence of an aluminum chloride catalyst and recovering there sultant condensation product.

Still another embodiment of this invention relates to a process whichcomprises condensing benzene with glucuronolactone in the presence of analuminum chloride The organic products threne,

2,938,911 Patented May 31, 196 0 catalyst and recovering the resultantcondensation product. 1

A still further embodiment of this invention is a product produced bycondensing benzene with glucuronolactone in the presence of aluminumchloride.

A still further embodiment of this invention is a mem ber of the groupconsisting of an aryl-l-desoxy-alduronolactone, anaryl-l-desoxy-alduronic acid, and a sodium salt of anaryl-l-desoxy-alduronic acid.

I have found that useful water-soluble and water-insoluble condensationproducts are formed by reacting lactones of sugar acids with aromatichydrocarbons in the presence of Friedel-Crafts metal halide catalysts,and particularly in the presence of aluminum chloride. Thesecondensation reaction are carried out conveniently in ordinary glassalkylation equipment using temperatures of from about 20 C. to about 150C., and preferably at temperatures of from about 20 C. to about C. Whilemany of the condensation reactions are carried out at substantiallyatmospheric pressure, it may be desirable in certain instances and withcertain reactants to carry out the reaction in metal autoclaves atpressures up to 100 atmospheres or more. It is convenient in mostinstances to operate the equipment utilized at the pressure generated bythe reaction mixture and catalyst contained therein at the temperatureutilized.

Aromatic hydrocarbons suitable for use as starting materials in theprocess of this invention include compounds containing only carbon andhydrogen and in which there is retained at least one hydrogen atomattached to a carbon atom of the aromatic nucleus. Thus compounds suchas hexamethylbenzene are excluded from the scope of the process of thepresent invention since such compounds are inoperative. The aromatichydrocarbons include those substituted with alkyl, aralkyl, aryl,alkaryl, cycloalkyl, alkylcycloalkyl, etc., radicals containing onlycarbon and hydrogen. So'me aromatic hydrocarbons may contain olefinicunsaturation or double bonds in the side chains or substituent groupscontaining only carbon and hydrogen and such compounds are within thegenerally broad scope of the present invention, but, however, suchcompounds are not preferred. Thus, the preferred aromatic hydrocarbonsare unsubstituted aromatic hydrocarbons, and aromatic hydrocarbonscontaining saturated or aromatic substituents containing only carbon andhydrogen. Aromatic hydrocarbons utilizable within the broad scope of theprocess of the present invention include benzene, toluene, ortho-xylene,meta-xylene, 1,2,3- trimethylbenzene, 1,2,4-trimethylbenzene,1,3,5-trimethylbenzene, 1,2,3.4-tetramethylbenzene,1,2,3,5-tetramethylbenzene, 1,2,4,S-tetramethylbenzene,pentamethylbenzene, ethylbenzene ortho-ethyltoluene, meta-ethyltoluene,paraethyltoluene, n-propylbenzene, isopropylbenzene, n-butylbenzene,isobutylbenzene, sec-butylbenzene, tert-butylbenzene, amylbenzenes,para-cymene, and higher molecular weight alkylaromatic hydrocarbons.Alkylaromatic hydrocarbons with long chain alkyl groups utilizable inthe process may be produced by the alkylation of aromatic hydrocarbonswith olefin polymers to yield such materials as hexylbenzenes,hexyltoluenes, nonylbenzenes, nonyltoluenes, dodecylbenzenes,dodecyltoluenes, etc. Often alkylate is obtained as a high boilingfraction in which case the alkyl group attached to the aromatichydrocarbon may contain from about 6 to about-24 carbon atoms.

Other aromatic hydrocarbons suitable for conversion into arylatedderivatives of lactones of sugar acids include those with two or morearyl groups such as diphenyl, diphenyl methane, triphenyl methane, etc.Examples of suitable utilizable aromatic hydrocarbons which containcondensed benzene rings include naphthalene, alphamethylnaphthalene,beta-methylnaphthalene, phenananthracene, naphthacene, pyrene, chrysine,I'ubrene, etc. Examples of other aromatic hydrocarbons utilizable in theprocess of the present invention include indan, fiuorene,cyclopentylbenzene, methylcyclopentylbenzene,- cyclohexylbenzene, etc.

The sugar acid lactones which are utilizable as starting materials inthe process of the present invention include both the alpha and betaforms of lyxuronolactone, arabinuronolactone, riburonolactone,taluronolactone, galacturonolactone, iduronolactone, guluronolactone,mannuronolactone, glucuronolactone, altruronolactone, alluronolact'one,etc. These internal esters of alduronic acids are spontaneously formedupon heating suitable alduronic acids in which formation of a 1-4 orgammalactone structure is possible, or in which formation of a 1-5 ordelta-lactone structure is possible. The alduronic acids are a group ofcompounds which are obtainable by oxidation of the terminal alcoholgroup of aldoses. The penturonic acids and their conversion topenturonolactones can be represented by the following general equation:

The hexuronic acids and their conversion to hexuronolactones can berepresented by the following general Since the alduronic acids mustcontain at least 5 carbon atoms to be able to form gamma-lactones, thesugar acid lactone-s which are preferred as starting materials in theprocess of this invention will contain at least 5 carbon atoms. Alsoutilizable are sugar acid lactones'containing 6 carbon atoms and more.When the sugar acid lactones react with aromatic hydrocarbons to formthe new compositions of matter of the present invention, they do so byreaction at the number 1 carbon atom, thus forming aryl derivatives oflactones of l-desoxy-uronic acids.

As an example of this process, glucuronolactone may be reacted with anequimolecular proportion or less of benzene to givemono-phenyl-desoxy-glucuronic and lactone or with more than anequimolecular proportion of benzene to give the lactone ofdi-phenyl-desoxy-glucur0nic acid. The structures of some of these arylhexuronic acid lactone reaction products are represented as follows:

An example of my di-aryl-hexuronic acid products is1,l-di-phenyl-l-desoxy-glucuronic acid represented by the followingstructural formula:

1,1-di-phenyl-1 desoxy-glucuromc acid Typical novel compositions ofmatter or new compounds which are prepared in accordance with theprocess of the present invention include l-phenyl- 1-desoxy-lyxuronolactone,

1, l-di-phenyl-l-desoxy-lyxuronolactone,l-phenyl-1-desoxy-xyluronolactone,

1, 1 -di-phenyll -desoxy-xyluronolactone, l-phenyl-1-desoxy-arabinuronolactone,

1, 1 -di-phenyl- 1-desoxy-arabinuronolactone,1-phenyl-1-desoxyrriburonolactone,

1, 1 -di-phenyl-l -desoxy-riburonolactone, l-phenyl- 1-desoxy-taluronolactone,

l l-di-phenyll -desoXy-taluronolactone, l-phenyl-1-desoxy-galacturonolactone,

1, l-di-phenyl-1-desoxy-galacturonolactonc,

l -phenyl-1 -desoxy-iduronolactone,

1 1-di-phenyl-l-desoxy-iduronolactone, l-phenyl- 1-desoxy-guluronolactone,

1 1 -di-phenyl-1 -desoxy-guluronolactone,l-phenyll-desoxy-mannuronolactone,

1 l-di-phenyll-desoxy-mannuronolactone,l-phenyl-1-desoxy-glucuronolactone,

l, 1 -di-phenyl-1-desoxy-glucuronolactone,

1 l-di-phenyl-l -'desoXy-altruronolactone,

1, l-di-phenyl-l-des oxy-altruronolactone,l-phenyl-1-desoxyra11uronolactone,

1 1 -di-phenyl 1 -desoxy-alluronolactone,

1 -p-tolyl-.1 -desoxy-lyxuronolactone,

1 1-di- (p-tolyl) -71-desoXy-lyxuronolactone, lr-p-tolyl-l-desoxy-xyluronolactone, 1,1-di-(p-tolyl) l-desoxy-xyluronolactone,1-p-tolyl-1-desoxy-arabinuronol actone, 1,1-di-(p-tolyl) l -desoxy-arabinuronolactone, l-p-tolyll-desoxy-riburonolactone,1,l-di-(p-tolyl)-1-desoxy-riburonolaetone,1-p-tolyl-1-desoxy-taluronolactone, 1,1-di-(p-tolyl)-1-desoxy-taluronolactone, l-p-tolyl-l -desoxygalacturonolaotone,1,1-di-(p-tolyl) -1-desoxy-galacturonolactone,1-p-tolyl-1-desoxy-iduronolactone,

1, l-di- (p-tolyl) -1-desoxy-iduronolactone,1-p-tolyl-1-desoxy-guluronolactone,

1 1 -di- (p-tolyl) -1-desoxy-guluronolactone,

1 -p-tolyl-1-desoxy-mannuronolactone,

1 l-di- (p-tolyl) l -desoxy-mannuronolactone,1-p-tolyl-l-desoxy-glucuronolactone,

1 ,1 -di-(p-*to1yl) 1 -desoxy-glucuronolactonc,

1 -p -tolyl-l-desoxy-altruronolactone,

1 l-di- (p-tolyl) 1 -desoxy-altruronolactone, l-p-tolyl-l-desoxyalluronolactone,

1,1-di- (p-tolyl) -1 desoxy-alluronolactone,

1-( 3 ,4-dimethylphenyl) -1-desoxy-lyxuronolactone, 1, 1-di-( 3,4-dimethylphenyl) l-desoxy-lyxuronolactone, 1-( 3 ,4-dimethylphenyl)-1-desoxy-xyluronolactone, 1 l-di- 3 ,4-dimethylphenyl)1-desoxy-xyluronolactone, 1- 3 ,4-dimethylphenyl)1-desoxy-arabinuronolactone,

the sodium salt of l-phenyl-1-desoxy-taluronic acid,

the sodium salt of 1,l-di phenyl-l-desoxy-taluronicEacid,

the sodium salt of l-phenyl-l-desoxy-galacturonic acid,

the sodium salt of 1,l-di-phenyl-*1adesoxy-galactui-onic acid,

the sodium salt of l-pheny1-1-desoxy-iduronic acid,

the sodium salt of l,l-diaphenyl-l-desoxy-iduronic the sodium salt of lpheiiyl-l-desoxy-guluronic .acid,

the sodium salt of 1,1-di-phenyl-l-desoxy-guluronic acid,

the sodium salt of l-phenyl-l-desoXy-mannuronic acid,

the sodium salt of l,l-di-phenyl-l-desoxy-mannuronic acid,

the sodium salt of 1-phenyl l-desoxy-glucuronic acid,

the sodium salt of 1,l-di-phenyl-l-desoxy-glucuronic acid,

the sodium salt of l-phenyl-l-desoxy-altruronic acid,

the sodium salt of 1,1-di-phenyl-l-desoxy-altruronic acid,

the sodium salt of 1-phenyl ldesoxy-alluronic acid,

the sodium salt of 1,l-di-phenyl-1-desoxy-alluronic acid,

the sodium salt of l-p-tolyl-l-desoxy-lyxuronic acid,

the sodium salt of 1,1-di-(p-toly'l)-1-desoxy-lyxuronic acid,

the sodium salt of .1 p-tolyl-Il-desoxy-xyluronic acid,

the sodium' salt of l,l-di-(p-tolyl) -l-desoxy-xyluronic acid,

the sodium salt of 1-p-tolyl-1-desoxy-arahinurouic acid,

the sodium salt of l,l-di-(p-tolyl)-1-desoxy-arahinuronic acid,

the sodium salt of l-p-tolyl-l-desoxy-1iburonic acid,

the sodium salt of '1,l-di-(p-t-olyl)-1-desoxy-riburonic acid,

the sodium salt of l-p-tolyl-l-desoxy-taluronic acid,

the sodium salt of 1,1-di-(p-tolyl) -1-desoxy-taluronic acid,

the sodium salt of l-p-tolyl-l-desoxy-galacturonic acid,

the sodium salt of l,1-;di-(p-tolyl)-1-desoxy-galacturonic acid,

the sodium salt of l-p-tolyl-l-desoxy-iduronic acid,

the sodium salt of 1,l-di-(p-tolyl)-1-desoxy iduronic acid,

the sodium salt of l-p-tolyl-l-desoxy-guluronic acid,

the salt of l,l-di-(p-tolyl)-1-desoxy-guluronic acid,

the sodium salt of 1-p-tolyl-l-desoxy-mannuronic acid,

the sodium salt of 1,1-di-(p-tolyl)l-desoxy-mannuronic acid,

the sodium salt of l-p-tolyl-l-desoxy-glucuronic acid,

the sodium salt of 1, l-di-(p-tolyl)-1-desoxy-glucuronic acid, I

the sodium salt of l-p tolyl-l-desoxy-alttjut'onic acid,

the sodium salt of 1,1-di-(p-tolyl)-1-desoxy-altruronic acid,

the sodium salt of l-p-tolyl-l-desoxy-alluronic acid,

the sodium salt of 1,1-di-.(p-tolyl)-1-desoxy-a1luronic acid,

the sodium salt of '1-(3,4-dimethy1pheny1)-1-desoxy-lyxu- Ionic acid, V

the sodium salt of 1,1-di-(3,4-dim'ethylphenyl):1-desoxylyxuronic acid,

the sodium salt of xyluronic acid,

the sodium salt of 1,l-di-(3,4-dimethylphenyl)-1-desoxyxyluronic acid,

the sodium salt of l-(3,4-dimethylpheny1)-1-desoxyarabinuronic acid,

the sodium salt of 1,1-di-(3,4-dimethylphenyl)-1-desoxyarabinuronicacid,

the sodium salt of 1-(3,4-dimethylphenyl)-1-desoxyriburonic acid,

the sodium salt of l,l-di-(3,4-dimethylphenyl)-l-desoxyriburonic acid,

the sodium salt of l-(3,4-dimethylphenyl) -l-desoxytaluronic' acid,

the sodium salt 'of 1,1-di-(3,4-dimethylphenyl)-l-desoxytalurouic acid,

the sodium salt of l-(3,4-dimethylphenyl)-1-desoxygalacturonic acid,

the sodium salt of 1,l-di-(3,4-dimethylphenyl) -l-desoxyj .galacturonicacid,

acid,

1- 3 ,4-dimcthy1phenyl) -1-desoxythe sodium .'-salt of1-(3.,4-dimethylphenyl)-l-desoxy iduronic acid, r

the sodium salt :of 1,l'-di (3,4 dimethylphenyb-l desoxyiduronic'racid,

the sodium salt of guluronic acid, H v

the sodium salt of .l,1-di-(3,4-dimethylphenyl) -l-desoxyguluronic acid,i i

the sodium salt of l-(3,4-dimethylphenyl)-l-desoxymannuronicacid, a V

the sodium-salt ofl,l-di-(3,4-dimethylphenyl)-1-desoxymannuronic acid,

the sodium salt of l-(3,4-dimethylphenyl)-1adesoxyglucuronic acid,

the sodium salt of 1,1-di-(.3,4-dimethylphenyl)-l desoxyglucuronic'acid, I

the sodium salt of, l-(3,4-dimethylpheny1)-1@desoxyaltruronic acid,

the sodium salt of l,1-di-(3,4-dimethylphenyl)-1 desoxyaltruronic acid,

the sodium salt of l-'(3,4-dimethylphenyl)-lvdesoxyalluronic acid, 7

the sodiumsalt :of l,l-di-(3,4-dimethylphenyl)-1-desoxyallurom'c acid,

the sodium salt of 1*p-ethylphenyl-l-desoxy-lyxuronic acid,

the sodium salt of l,l-di-(p-ethylphenyl)-l-desoxylyxuronic acid, e

the sodium salt acid,

the sodium of l-p-ethylpheny1-l-desoxy-xyluronic salt of1,1-di-(p-ethylphenyl)-1-desoxyxylmonic acid, a

the stadium salt of 1-p-ethylphenyl-l-desoxy-arabinuronic aci the sodiumsalt of 1,1-di-(p-ethylpheuyl)-l-desoxyarabinuronic acid, V

the sgdium salt of l-p-ethyl-phenyl-l-desoxy-riburonic the sodium saltof l,l-di-(p-ethylphenyl)-1-desoxyriburonic acid,

the sodium salt of 1-p-ethylphenyl-l-desoxy-taluronic aci the sodiumsalt of 1,1-di-(p-ethylphenyl)-1-desoxytaluronic acid,

the sodium salt of 1-p-ethylphenyl-l-desoxy-galacturonic acid,

the sodium salt of galacturonic acid,

the saodium salt of 1 p-ethylphenyl-l-desoxy-iduronic aci the sodiumsalt of iduronic acid,

the sodium salt of 'l-p-ethylphenyl-l-desoxy-guluronic act the sodiumsalt guluronic acid,

the sodium salt of acid,

the sodium salt mannuronic acid,

the sgdium salt of 1-p-ethylpheny1-l-desoxy-glucuronic aci the sodiumsalt of 1,1-di-(p-ethylphenyl)-1-desoxyglucuronic acid,

the sodium salt of l-p-ethylphenyl-l-desoxy-altruronic acid,

the sodium salt of 1,1-di-(p-ethylphenyl)-1-desoxy altruronic acid,

the sodium salt of 1-p-ethylpheny1-1-desoxy-alluronic acid, and V thesodium salt of 1,1-di-(p-ethylphenyl)-1-desoxyalluIonic acid.YFriedeI-Crafts metal halide catalysts which are employed in thisprocess are used in substantially anhydrous form or modified by means ofan alcohol, an ether,

1 l-di-(p -ethj lphenyl) -1 -desoxy- 1,1-di-(p-ethylphenyl) -1-desoxyo't 1,1-di-(p ethy1phenyl)-1-desoxy-1-p-ethylphenyl-l-desoxy-mannuronic of 1,l-di-(p-ethylphenyD-l-dmoxyanester, a nitroparaflin, etc. to give a catalyst of controlled activity,if so desired. A Friedel-Crafts metal halide catalyst which is preferredfor use in this process is substantially anhydrous aluminum chloride.Other Friedel-Crafts metal halides which may be utilized as catalysts inthis process, but not necessarily with equivalent results, are aluminumbromide, ferric chloride, ferric bromide, zinc chloride, berylliumchloride, gallium chloride, titanium tetrachloride, zirconium chloride,stannic chloride, etc.

The process may be carried out by slowly adding a Friedel-Crafts metalhalide catalyst such as aluminum chloride to a stirred mixture of anaromatic hydrocarbon and sugar acid lactone while maintaining thereaction temperature at from about 20 C. to about 150 C. and preferablyat from about 20 C. to about 100 C. After the reaction mixture hasreached the desired degree of reaction or completion, the. entirereaction mixture and catalyst may be mixed with water or may be added toice in order to quench the activity of the catalyst and to permitseparation of the organic reaction product and unreacted startingmaterials.

The nature of this invention is illustrated further by the followingexample, which, however, should not be construed to limit unduly thegenerally broad scope of the invention.

During the contacting, 29 grams of HCl was evolved. The flask contentswas decomposed with ice and the following recovery noted exclusive ofunreacted benzene:

Grams Hydrocarbon soluble oil 4.2 Water washed, cold water insolublesolid (A) 54 Segment (A) was boiled with caustic solution, the insolublepart filtered off; the filtrate acidified, throwing down precipitate(B); the filtrate from (B) was ether extracted to give solid (C).

Pure compounds isolated (l) m m s Segment (B) contained 12 grams of acomponent, (1), insoluble in cold water and crystallizing from hot waterin needles forming star clusters. Dried on a filter paper, thesecrystals showed a slight yellow sheen, and melted at 178-l80 C. Thesecrystals dissolved immediately in NaOH solution but in concentratedsolution separated immediately as a sodium salt in the form of shortneedles melting at 205-210 C. with decomposition. The sodium saltdissolved when diluted with water; when this solution was acidified, noimmediate precipitation occurred, but in 2 to 3 days, needles came outmelting at 179-180 C., identical to the original. The compound burnedwith difliculty and difliculty was observed in carbon and hydrogenanalysis in obtaining complete combustion.

Elementary analysis of (1) Thus, elementary analysis and chemicalbehaviorof product,(l) are in accord with1,1-diphenyl-l-desoxyglucuronolactone:

1,1-diphenyl-1-desoxyhexuronplactona Glucuronolactone does not exist asthe free acid, and the lactone structure apparently went through thereaction and subsequent water recrystallizations unchanged.

Segment (C) crystallized from ether to crystals, designated (2), ofmelting point 138-139" C. This product had a fatty acid odor and gave afoamy solution in water. Like compound (1), it burned with difliculty.

The yield of compound (2) could not be evaluated from the dataavailable; its yield, however, was substantially less than that of (1).0n the basis of analysis, chemical behavior, and fatty acid odor, (2)corresponds to the free acid of which (1) is the lactone.

Ht'JOH KOCH H OH H OH

0 0H 1,1-dl-phenyl-1-dssoxyhexuronic acid EXAMPLE II The sodium salt ofcompound 1, as described in Example I, was prepared by reaction of1,1-di-phenyl-1- desoxyglucuronolactone with an ethanolic solution ofsodium hydroxide. The sodium salt is a solid and was recovered byfiltration. This sodium salt was tested as a corrosion inhibitor in 300cc. of a 5% sodium chloride solution. The concentration of this sodiumsalt of 1,1- di-phenyl-l-desoxy-glucuronic acid utilized was 0.05 weightpercent in the sodium chloride solution.

The corrosion inhibitor was evaluated by adding the 300 cc. of 5% sodiumchloride solution containing 0.05% of the inhibitor into a 600 cc.beaker which was stirred at 250 r.p.m. and air bubbled therethrough at arate of 5.6 liters per hour. On the bottom of the beaker in contact withthe brine solution was a mild steel strip one end of which was elevatedby a glass rod. Stirring and air introduction was continued for 6 hourstime. At the same time a duplicate experiment was. carried out with noadded corrosion inhibitor in the brine solution. The iron strip in theblank or control experiment lost 22 milligrams in weight during the runin comparison to a weight loss of 7.5 milligrams for the iron stripin'contact with the brine solution and the sodium salt of1,1-di-phenyl-ldesoxy-glucuronic acid.

These experiments show that 1,1-di-phenyl-1-desoxyglucuronic acid in theform of its sodium salt is equivalent to or slightly better than sodiumnitrite, a well known corrosion inhibitor. The addition of the sameconcentration of sodium nitrite to a brine solution results in a weightloss of 8 milligrams in a comparable corrosion test. Water solublecorrosion inhibitors for brine solutions are particularly important foruse by railroads since brine which drips from refrigerator cars causesserious corrosion of railroad tracks. Also, water soluble corrosioninhibitors are important in other diverse uses such as in boiler water,etc.

I claim as my invention:

1. A compound selected from the group consisting of aryl-l-desoxyalduronolactone, aryl-l-desoxy alduronic acid, and a sodium salt ofaryl-l-desoxy-alduronic acid.

. Phenyl-Ldcsoxy-alduronolactone. Bhenyl-l-desoxy-hexuronolactone.

l-phenyll-desoxy-glucuronolactone Il,l-di-phenyl-1-desoxy-glucuronolactone. Phenyl-ledesoxy-alduronic acid.Phenyl-l-desoxy-hexuronic acid.

l-phenyl-l-desoxy-glucuronic acid. I 9; l,l-diphenyl-l-desoxy-glucuronic acid.

1 0. The sodium salt of phenyl-l-desoxy-alduronic acid. 11. The sodiumsalt of phenyl-l-desoxy-hexuronic acid.

12. The sodium salt of 1-phenyl-l-desoxy-glucuronic acid. a

13. Thesodium salt of 1,1-di-phenyl-l-desoxyglucuronic acid. I

References Cited in the file of this patent UNITED STATES PATENTS BonnerJune 7, 1949 2,798,098 Linn July 2, 1957 2,798,100 Linn July 2, 1957

1. A COMPOUND SELECTED FROM THE GROUP CONSISTING OF ARYL-1-DESOXYALDURONOLACTONE, ARYL-1-DESOXY ALDURONIC ACID, AND A SODIUM SALT OFARYL-1-DESOXY-ALDURONIC ACID.
 4. 1-PHENYL-1-DESOXY-GLUCURONOLACTONE.